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High-level vibrational calculations have been used to investigate anharmonicity in a wide variety of materials using density-functional-theory (DFT) methods. We have developed a new and efficient approach for describing strongly-anharmonic…

Materials Science · Physics 2017-06-20 Joseph C. A. Prentice , R. J. Needs

We propose a new variational Monte Carlo (VMC) method with an energy variance extrapolation for large-scale shell-model calculations. This variational Monte Carlo is a stochastic optimization method with a projected correlated condensed…

Nuclear Theory · Physics 2012-02-14 Takahiro Mizusaki , Noritaka Shimizu

We study three wave function optimization methods based on energy minimization in a variational Monte Carlo framework: the Newton, linear and perturbative methods. In the Newton method, the parameter variations are calculated from the…

Chemical Physics · Physics 2015-06-26 Julien Toulouse , C. J. Umrigar

We present a variational Monte Carlo (VMC) method that works equally well for the ground and the excited states of a quantum system. The method is based on the minimization of the variance of energy, as opposed to the energy itself in…

Computational Physics · Physics 2007-05-23 Imran Khan , Bo Gao

Certain point defects in solids can efficiently be used as qubits for applications in quantum technology. They have spin states that are initializable, readable, robust, and can be manipulated optically. New theoretical methods are needed…

Computational Physics · Physics 2023-09-20 Kristoffer Simula , Ilja Makkonen

Variational methods are used to calculate structural and thermodynamical properties of a titrating polyelectrolyte in a discrete representation. The Coulomb interactions are emulated by harmonic repulsive forces, the force constants being…

chem-ph · Physics 2008-02-03 B. Jönsson , M. Ullner , C. Peterson , O. Sommelius , B. Söderberg

Computation of ionic forces using quantum Monte Carlo methods has long been a challenge. We introduce a simple procedure, based on known properties of physical electronic densities, to make the variance of the Hellmann-Feynman estimator…

Computational Physics · Physics 2007-05-23 Simone Chiesa , David Ceperley , Shiwei Zhang

We review the use of continuum quantum Monte Carlo (QMC) methods for the calculation of energy gaps from first principles, and present a broad set of excited-state calculations carried out with the variational and fixed-node diffusion QMC…

Materials Science · Physics 2018-08-22 Ryan J. Hunt , Marcin Szyniszewski , Genki I. Prayogo , Ryo Maezono , Neil D. Drummond

Modern quantum Monte Carlo (QMC) methods often capture electron correlation through both explicitly correlating Jastrow factors and small to mid-sized configuration interaction (CI) expansions. Here, we study the additional optimization…

Chemical Physics · Physics 2023-02-08 Scott M. Garner , Eric Neuscamman

Quantum mechanics for many-body systems may be reduced to the evaluation of integrals in 3N dimensions using Monte-Carlo, providing the Quantum Monte Carlo ab initio methods. Here we limit ourselves to expectation values for trial…

Computational Physics · Physics 2010-11-22 John Robert Trail , Ryo Maezono

A faithful description of chemical processes requires exploring extended regions of the molecular potential energy surface (PES), which remains challenging for strongly correlated systems. Transferable deep-learning variational Monte Carlo…

Chemical Physics · Physics 2026-03-27 P. Bernát Szabó , Zeno Schätzle , Frank Noé

An algorithm is proposed to optimize quantum Monte Carlo (QMC) wave functions based on New ton's method and analytical computation of the first and second derivatives of the variati onal energy. This direct application of the variational…

Chemical Physics · Physics 2016-09-08 Xi Lin , Hongkai Zhang , Andrew M. Rappe

The detection of vibrational excitations of individual molecules on surfaces by scanning tunneling spectroscopy does not obey strict selection rules but rather propensity rules. The experimental verification of these is challenging because…

Despite vibrational properties being critical for the ab initio prediction of the finite temperature stability and transport properties of solids, their inclusion in ab initio materials repositories has been hindered by expensive…

Machine learning over-fitting caused by data scarcity greatly limits the application of machine learning for molecules. Due to manufacturing processes difference, big data is not always rendered available through computational chemistry…

Machine Learning · Computer Science 2020-11-20 Ziyang Zhang , Yingtao Luo

Variational wave functions used in the variational Monte Carlo (VMC) method are extensively improved to overcome the biases coming from the assumed variational form of the wave functions. We construct a highly generalized variational form…

Strongly Correlated Electrons · Physics 2008-10-27 Daisuke Tahara , Masatoshi Imada

We study the potential energy surface of the ozone molecule by means of Quantum Monte Carlo simulations based on the resonating valence bond concept. The trial wave function consists of an antisymmetrized geminal power arranged in a…

Computational Physics · Physics 2016-08-23 Sam Azadi , Ranber Singh , Thomas D. Kühne

We use a variational Monte Carlo algorithm to solve the electronic structure of two-dimensional semiconductor quantum dots in external magnetic field. We present accurate many-body wave functions for the system in various magnetic field…

Mesoscale and Nanoscale Physics · Physics 2009-11-11 Ari Harju

When using Hartree-Fock (HF) trial wave functions in quantum Monte Carlo calculations, one faces, in case of HF instabilities, the HF symmetry dilemma in choosing between the symmetry-adapted solution of higher HF energy and symmetry-broken…

Chemical Physics · Physics 2011-07-19 Peter Reinhardt , Julien Toulouse , Roland Assaraf , C. J. Umrigar , Philip E. Hoggan

We study the effects of atomic vibrations on the solid-state chemical shielding tensor using first principles density functional theory calculations. At the harmonic level, we use a Monte Carlo method and a perturbative expansion. The Monte…

Materials Science · Physics 2014-10-07 Bartomeu Monserrat , Richard J. Needs , Chris J. Pickard